Isobutyl substituted heterocyclic compounds for augmenting or enhancing the organoleptic properties of smoking tobaccos and smoking tobacco articles

ABSTRACT

Processes and compositions are described for the use in smoking tobacco flavor and aroma augmenting, modifying, enhancing and imparting compositions and as smoking tobacco aroma or flavor imparting, augmenting or enhancing materials of a mixture of compounds having the generic structure: ##STR1## wherein X is a moiety selected from the group consisting of: ##STR2## and wherein R 1  and R 2  are different, one of R 1  or R 2  being methyl, and the other of R 1  or R 2  being ethyl, or mixtures of same, including (i) 2,4,6-triisobutyl-1,3,5-trioxane and (ii) 2-isobutyl dialkyloxazolines.

This application is a divisional of application for United StatesLetters Patent Ser. No. 807,056, June 16, 1977, now U.S. Pat. No.4,093,752, issued on June 6, 1978.

BACKGROUND OF THE INVENTION

The present invention relates to a genus of compounds having the genericstructure: ##STR3## wherein X is a moiety selected from the groupconsisting of ##STR4## and wherein R₁ and R₂ are different, one of R₁ orR₂ being methyl, and the other of R₁ or R₂ being ethyl, or mixtures ofsame, and novel compositions using members of such genus of compounds ormixtures of same to augment, modify or enhance the flavor and/or aromaof consumable materials or impart flavor and/or aroma to consumablematerials.

There has been considerable work performed relating to substances whichcan be used to impart (modify, augment or enhance) flavors and aromas to(or in) various consumable materials such as foodstuffs havingchocolate, cocoa butter, milk, vanilla, blackberry, cooked vegetable,stew, cooked green vegetable and baked goods flavors and tobaccos whichhave been produced from reconstituted tobacco having imparted theretodistinctive, pleasing chocolate flavor nuances, or tobaccos havingnutty, green and burnt roasted flavor and aroma chatacteristics prior toand on smoking. These substances are used to diminish the use of naturalmaterials, some of which may be in short supply, and to provide moreuniform properties in the finished product.

Sweet, dairy-like, creamy, vanilla, berry, milk chocolate-like,chocolate, green pepper, cooked green pepper, spicey, peppery, meaty,roasted, and cocoa butter-like aromas as well as sweet, dairy-like,creamy, vanilla, berry, milk chocolate, green pepper, cooked greenpepper, nutty, spicey, peppery, meaty, roasted, chocolate and cocoabutter-like flavor characteristics are particularly desirable for manyuses in foodstuff flavors, chewing gum flavors, toothpaste flavors, andmedicinal product flavors.

Chocolate-like aromas with cocoa-like and sweet, creamy nuances ornutty, green, burnt roasted aromas prior to smoking, and chocolate-likearoma notes and more tobacco-like smoke aroma characteristics in themain stream and side stream on smoking are desirable in tobaccos and intobacco flavoring compositions.

German Auslegschrift No. 2,402,416 discloses a sublimable performedcomposition in tablet form containing 1,3,5-triisopropyl-s-trioxane or1,3,5-tri-t-butyl-s-trioxane as an active agent whereby the compositionmay be used to deodorize toilets, telephone mouthpieces, or give offinsecticides.

2,4,6-Tri-s-butyl-1,3,5-trioxane is disclosed at Volume 19, page 391 ofBeilstein; and it is further disclosed to be a "trimer" of methyl ethylacetaldehyde (2-methyl butanal). An additional disclosure in Beilsteinis at Volume 19, supplement 2 at page 403. Neither Beilstein referencediscloses the organoleptic qualities of2,4,6-triisobutyl-1,3,5-trioxane.

Indeed, the 1,3,5-triisopropyl-s-trioxane has little, if any, aroma orflavor to be of value in flavoring foodstuffs or tobaccos. It is,accordingly, quite surprising that the next adjacent methyl homologue,2,4,6-triisobutyl-1,3,5-trioxane, has such intense aroma and flavornuances as described herein.

Trialkyl substituted oxazolines are described in the prior art as beinguseful for modifying fish flavors in U.S. Pat. No. 3,627,540 issued onDec. 14, 1971. More specifically, it is stated at Column 2, lines 12-27:

The seafood flavor characteristic of the pentadienal can further bevaried by including one or more cyclic oxazo compounds, particularly Δ³-oxazolines having the formula ##STR5## wherein R₁, R₂ and R₃ arehydrogen, alkyl, or alkylene and can be the same or different. It ispreferred in certain embodiments of the present invention to use loweralkyl derivatives of oxazoline, preferably those having up to aboutthree carbon atoms in the alkyl group or groups. A preferred oxazolinein certain embodiments of the invention is 2,4,5-trimethyl-Δ³-oxazoline. U.S. Pat. No. 3,627,540 does not imply, however, that thehigher alkyl oxazoline analogue of the instant invention taken alone orin admixture with the 2,4,6-triisobutyl-1,3,5-trioxane of our invention,have flavor and aroma nuances of such quality and intensity as describedherein.

Mussinan et al, "Identification and Flavor Properties of Some3-Oxazolines and 3-Thiazolines Isolated from Cooked Beef," Abstracts ofPapers, 170th Meeting, American Chemical Society, August 24-29, 1975,Port City Press, Baltimore, Maryland, Item No. AGFD 022, states:

²². IDENTIFICATION AND FLAVOR PROPERTIES OF SOME 3-OXAZOLINES AND3-THIAZOLINES ISOLATED FROM COOKED BEEF. Cynthia J. Mussinan, Richard A.Wilson, Ira Katz, Anne Sanderson, and Manfred H, Vock. InternationalFlavors and Fragrances, Inc., 1515 Highway 36, Union Beach, New Jersey07735.

Four 3-oxazolines and two 3-thiazolines have been isolated from beefcooked in a sealed stainless steel vessel at 162.7° and 182°. Thecompounds were identified by matching retention times and mass spectrawith those of authentic compounds synthesized in our laboratory. Thecompounds identified were 2,4-dimethyl-3-oxazoline;2,4,5-trimethyl-3-oxazoline; 2,4-dimethyl-5-ethyl-3-oxazoline;2,5-dimethyl-4-ethyl-3-oxazoline; 2,4-dimethyl-3-thiazoline; and2,4,5-trimethyl-3-thiazoline. The synthesis, spectra and flavorproperties of these and some related compounds will be discussed. Noneof the oxazoline compounds of Mussinan et al. have properties evenremotely similar to those of the compounds containing the oxazolinemoieties of the instant invention. Thus, the compounds containing theoxazoline moieties of the instant invention have unexpected, unobviousand advantageous properties with respect to their organolepticcharacteristics when compared with the oxazolines of Mussinan et al. andU.S. Pat. No. 3,627,540.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 represents the NMR spectrum for 2,4,6-triisobutyl-1,3,5-trioxaneproduced according to Example I.

FIG. 2 represents the infrared spectrum for2,4,6-triisobutyl-1,3,5-trioxane produced according to Example I.

FIG. 3 represents the mass spectrum for 2,4,6-triisobutyl-1,3,5-trioxaneproduced according to Example I.

FIG. 4 represents the NMR spectrum for5-ethyl-4-methyl-2-isobutyl-3-oxazoline (fraction 2-5, peak 2) producedaccording to Example II.

FIG. 5 represents the infrared spectrum for5-ethyl-4-methyl-2-isobutyl-3-oxazoline (fraction 2-5, peak 2) producedaccording to Example II.

FIG. 6 represents the mass spectrum for5-ethyl-4-methyl-2-isobutyl-3-oxazoline produced according to ExampleII.

FIG. 7 represents the NMR spectrum for4-ethyl-5-methyl-2-isobutyl-3-oxazoline (fraction 2-5, peak 1) producedaccording to Example II.

FIG. 8 represents the infrared spectrum for4-ethyl-5-methyl-2-isobutyl-3-oxazoline (fraction 2-5, peak 1) producedaccording to Example II.

FIG. 9 represents the mass spectrum for4-ethyl-5-methyl-2-isobutyl-3-oxazoline produced according to ExampleII.

THE INVENTION

It has now been discovered that novel solid and liquid foodstuff,chewing gum, medicinal product and toothpaste compositions and flavoringcompositions therefor having sweet, dairy-like, creamy, vanilla, berry,milk chocolate-like, chocolate, green pepper, cooked green pepper,spicey, peppery, meaty, roasted and cocoa butter-like aromas and sweet,dairy-like, creamy, vanilla, berry, milk chocolate-like, green pepper,cooked green pepper, nutty, spicey, peppery, meaty, roasted, chocolate,and cocoa butter-like flavor characteristics; as well as novel tobaccoand tobacco flavoring compositions having chocolate-like, cocoa-like,nutty, green, burnt roasted, and sweet, creamy aromas prior to smokingand chocolate-like aroma notes and more tobacco-like aroma notes onsmoking in the main stream and in the side stream may be provided by theutilization of a genus of compounds having the generic structure:##STR6## wherein X is a moiety selected from the group consisting of##STR7## wherein R₁ and R₂ are different and each is selected from thegroup consisting of ethyl and methyl or mixtures of same, that is (i)2,4,6-triisobutyl-1,3,5-trioxane having the structure: ##STR8## (ii)2-isobutyl dialkyl oxazolines having the generic structure: ##STR9##wherein R₁ and R₂ are different and are each selected from the groupconsisting of methyl and ethyl or (iii) mixtures of said trioxane andone or more of said oxazolines in foodstuffs, chewing gums, toothpastes,medicinal products, and tobaccos as well as tobacco substitutes.

2,4,6-Triisobutyl-1,3,5-trioxane useful as indicated supra, may beproduced, preferably, by one of several processes.

A preferred process comprises the trimerization of isovaleraldehyde inthe presence of an acidic catalyst.

More specifically, this process comprises the reaction step: ##STR10##

This reaction takes place in the presence of a mineral acid catalystsuch as concentrated sulfuric acid or concentrated phosphoric acid. Thereaction also takes place in the presence of an inert solvent such asbenzene, toluene or xylene. The weight ratio of isovaleraldehyde:solventmay vary from 0.5:1 up to about 5:1 with a preferable weight ratio ofabout 2:1. The percentage of concentrated acid catalyst in the reactionmass may vary from 0.5% by weight of acid catalyst based onisovaleraldehyde up to 4% by weight of acid catalyst based onisovaleraldehyde. The reaction temperature may vary from about 0° C. upto about 25° C. with a preferable reaction temperature range of fromabout 5° C. up to about 12° C.

The reaction time is preferably in the range of from 15 hours up to 30hours.

At the end of the reaction the acidic catalyst is neutralized with basesuch as sodium hydroxide, potassium hydroxide, sodium carbonate orpotassium carbonate. The reaction mass is then washed to neutral withwater, and the resultant product is distilled.2,4,6-Triisobutyl-1,3,5-trioxane may be distilled at 95° C. and 1 mm Hgpressure without any decomposition of the resultant product.

The genus of compounds having the generic structure: ##STR11## wherein Xis one of the moieties selected from the group consisting of ##STR12##and wherein R₁ and R₂ are different and each is selected from the groupconsisting of methyl and ethyl, is prepared by a novel process whichinvolves first reacting isovaleraldehyde with aqueous ammonia to formthe isovaleraldehyde imine and then reacting the resultingisovaleraldehyde imine with 2(3)-hydroxy-3(2)-pentanone to form themixture of oxazolines as well as 2,4,6-triisobutyl-1,3,5-trioxaneaccording to the following reaction sequence: ##STR13##

The first reaction, that of aqueous ammonia with isovaleraldehyde,preferably takes place at a temperature in the range of from about 0° C.up to about 10° C. It is most convenient and most preferable to carryout the reaction using a mole ratio of ammonia:isovaleraldehyde of 1:1although mole ratios of from 0.5:1 up to 2:1 of isovaleraldehyde:ammoniamay be used.

The resulting imine may then be reacted with either2-hydroxy-3-pentanone or 3-hydroxy-2-pentanone or a mixture thereof.This reaction preferably takes place at a temperature in the range offrom about 30° C. up to about 50° C. with a preferable temperature rangeof from 35° up to 40° C. The time of reaction varies with thetemperature with the shorter times of reaction being satisfactory ifgreater temperatures of reaction are used. The most preferred time ofreaction is 2 hours using a temperature of from 35°-40° C., but times ofreaction of from 1 up to 10 hours are useful.

At the end of the second reaction wherein the oxazolines are formed, thereaction mass is extracted with an inert solvent such as diethyl ether,the organic extract is evaporated and the resulting material isdistilled. Preparative GLC may then be used in order to separate theoxazolines from the 2,4,6-triisobutyl-1,3,5-trioxane.

The compounds having the generic structure: ##STR14## wherein X is:##STR15## and wherein R₁ and R₂ are different and each represents ethylor methyl, that is the compounds (i) 2,4,6-triisobutyl-1,3,5-trioxane,or (ii) 2-isobutyl dialkyl oxazolines or (iii) mixtures of said trioxaneand said oxazolines, having the following organoleptic properties:

                                      Table I                                     __________________________________________________________________________                               Organoleptic                                                                             Organoleptic                                                       Properties as                                                                            Properties as                           Name of Compound                                                                        Structure        Food Flavor                                                                              Tobacco Flavor                          __________________________________________________________________________    2,4,6-triisobutyl- 1,3,5-trioxane                                                        ##STR16##       Sweet, dairy-like, creamy, vanilla, berry-like,                                milk chocolate-like and cocoa butter-like                                    aroma and a sweet, dairy-like, creamy,                                        vanilla, berry, milk chocolate-like and cocoa                                 butter-like flavor at 15 ppm                                                             A chocolate-like, cocoa-like and                                              sweet, creamy aroma and flavor                                                prior to smoking and a                                                        chocolate-like aroma and more                                                 tobacco- like nuances on smoking in                                           the main stream and side stream.        5-ethyl-2-isobutyl- 4-methyl-3-oxazoline                                                 ##STR17##       Cooked green pepper, spicey, peppery and meaty                                aroma with cooked green pepper, spicey,                                       peppery and meaty flavor charac- teristics at                                 10 ppm.    Green pepper-like and slight                                                  vegetable-like aroma                                                          characteristics prior to and on                                               smoking in the main stream and the                                            side stream.                            4-ethyl-2-isobutyl-5- methyl-3-oxazoline                                                 ##STR18##       Green pepper, chocolate and roasted aroma                                     characteristic with green pepper, hydrolyzed                                  vegetable protein mouthfeel, and chocolate,                                   nutty, and roasted notes at 6                      __________________________________________________________________________                               ppm.       Chocolate-like, nutty, green, burnt                                           roasted- like aroma prior to                                                  smoking and on smoking in the main                                            stream and in the side stream.      

When the isobutyl substituted heterocyclic compounds and/or mixtures ofsame of our invention are used as a food flavor adjuvant, the nature ofthe co-ingredients included with the said isobutyl substitutedheterocyclic compounds and/or mixtures of same in formulating theproduct composition will also serve to alter, modify, augment or enhancethe organoleptic characteristics of the ultimate foodstuff treatedtherewith.

As used herein in regard to flavors, the terms "alter", "modify" and"augment" in their various forms mean "supplying or imparting flavorcharacter or note to otherwise bland, relatively tasteless substances oraugmenting the existing flavor characteristic where a natural flavor isdeficient in some regard or supplementing the existing flavor impressionto modify its quality, character or taste".

The term "enhance" is used herein to mean the intensification of aflavor or aroma characteristic or note without the modification of thequality thereof. Thus, "enhancement" of a flavor or aroma means that theenhancement agent does not add any additional flavor note.

As used herein, the term "foodstuff" includes both solid and liquidingestible materials which usually do, but need not, have nutritionalvalue. Thus, foodstuffs include soaps, convenience foods, beverages,dairy products, candies, vegetables, cereals, soft drinks, snacks andthe like.

As used herein, the term "medicinal product" includes both solids andliquids which are ingestible non-toxic materials which have medicinalvalue such as cough syrups, cough drops, aspirin and chewable medicinaltablets.

The term "chewing gum" is intended to mean a composition which comprisesa substantially water-insoluble, chewable plastic gum base such aschicle, or substitutes therefor, including jelutong, guttakay, rubber orcertain comestible natural or synthetic resins or waxes. Incorporatedwith the gum base in admixture therewith may be plasticizers orsoftening agents, e.g., glycerine; and a flavoring composition whichincorporates one or more of the enol esters of our invention, and inaddition, sweetening agents which may be sugars, including sucrose ordextrose and/or artificial sweeteners such as cyclamates or saccharin.Other optional ingredients may also be present.

Substances suitable for use herein as co-ingredients or flavoringadjuvants are well known in the art for such use, being extensivelydescribed in the relevant literature. It is a requirement that any suchmaterial be "ingestibly" acceptable and thus non-toxic and otherwisenon-deleterious particularly from an organoleptic standpoint whereby theultimate flavor and/or aroma of the consumable material used is notcaused to have unacceptable aroma and taste nuances. Such materials mayin general be characterized as flavoring adjuvants or vehiclescomprising broadly stabilizers, thickeners, surface active agents,conditioners, other flavorants and flavor intensifiers.

Stabilizer compounds include preservatives, e.g., sodium chloride;antioxidants, e.g., calcium and sodium ascorbate, ascorbic acid,butylated hydroxy-anisole (mixture of 2- and3-tertiary-butyl-4-hydroxy-anisole), butylated hydroxy toluene(2,6-di-tertiary-butyl-4-methyl phenol), propyl gallate and the like andsequestrants, e.g., citric acid.

Thickener compounds include carriers, binders, protective colloids,suspending agents, emulsifiers and the like, e.g., agar agar,carrageenan; cellulose and cellulose derivatives such as carboxymethylcellulose and methyl cellulose; natural and synthetic gums such as gumarabic, gum tragacanth; gelatin, proteinaceous materials; lipids;carbohydrates; starches, pectins, and emulsifiers, e.g., mono- anddiglycerides of fatty acids, skim milk powder, hexoses, pentoses,disaccharides, e.g., sucrose corn syrup and the like.

Surface active agents include emulsifying agents, e.g., fatty acids suchas capric acid, caprylic acid, palmitic acid, myristic acid and thelike, mono- and diglycerides of fatty acids, lecithin, defoaming andflavor-dispersing agents such as sorbitan monostearate, potassiumstearate, hydrogenated tallow alcohol and the like.

Conditioners include compounds such as bleaching and maturing agents,e.g., benzoyl peroxide, calcium peroxide, hydrogen peroxide and thelike; starch modifiers such as peracetic acid, sodium chlorite, sodiumhypochlorite, propylene oxide, succinic anhydride and the like, buffersand neutralizing agents, e.g., sodium acetate, ammonium bicarbonate,ammonium phosphate, citric acid, lactic acid, vinegar and the like;colorants, e.g., carminic acid, cochineal, tumeric and curcuma and thelike; firming agents such as aluminum sodium sulfate, calcium chlorideand calcium gluconate; texturizers, anti-caking agents, e.g., aluminumcalcium sulfate and tribasic calcium phosphate; enzymes; yeast foods,e.g., calcium lactate and calcium sulfate; nutrient supplements, e.g.,iron salts such as ferric phosphate, ferrous gluconate and the like,riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfateand the like.

Other flavorants and flavor intensifiers include organic acids, e.g.,acetic acid, formic acid, 2-hexenoic acid, benzoic acid, n-butyric acid,caproic acid, caprylic acid, cinnamic acid, isobutyric acid, isovalericacid, alpha-methyl-butyric acid, propionic acid, valeric acid,2-methyl-2-pentenoic acid, and 2-methyl-cis-3-pentenoic acid; ketonesand aldehydes, e.g., acetaldehyde, acetophenone, acetone, acetyl methylcarbinol, acrolein, n-butanal, crotonal, diacetyl, 2-methyl butanal,beta,beta-dimethyl-acrolein, methyl-n-amyl ketone, n-hexanal, 2-hexenal,iso-pentanal, hydrocinnamic aldehyde, cis-3-hexenal, 2-heptanal, nonylaldehyde, 2-phenyl-2-butenal, 4-methyl-2-phenyl-2-pentenal,5-methyl-2-phenyl-2-hexenal, 4-(p-hydroxyphenyl)-2-butanone,alpha-ionone, beta-ionone, 2-methyl-3-butanone, benzaldehyde, damascone,damascenone, 2-heptanone, o-hydroxyacetophenone,2-methyl-2-hepten-6-one, 2-octanone, 2-undecanone, 3-phenyl-4-pentenal,2-phenyl-4-pentenal, 2-phenyl-2-hexenal, 2-phenyl-2-pentenal, furfural,5-methyl-furfural, cinnamaldehyde, isovaleraldehydebeta-cyclohomocitral, 2-pentanone, 2-pentenal and propanal; alcoholssuch as 1-butanol, benzyl alcohol, 1-borneol, trans-2-buten-1-ol,ethanol, geraniol, 1-hexanol, 2-heptanol, trans-2 -hexenol-1,cis-3-hexen-1-ol, 3-methyl-3-buten-1-ol, 1-pentanol, 1-penten-3-ol,p-hydroxyphenyl-2-ethanol, isoamyl alcohol, isofenchyl alcohol,2-phenylethanol, alpha-terpineol, cis-terpineol hydrate, eugenol,linalool, acetoin; esters, such as butyl acetate, ethyl acetate, ethylacetoacetate, ethyl benzoate, ethyl butyrate, ethyl caprate, ethylcaproate, ethyl caprylate, ethyl cinnamate, ethyl crotonate, ethylformate, ethyl isobutyrate, ethyl isovalerate, ethyl laurate, ethylmyristate, ethyl alpha-methylbutyrate, ethyl propionate, ethylsalicylate, trans-2-hexenyl acetate, hexyl acetate, 2-hexenyl butyrate,hexyl butyrate, isoamyl acetate, isopropyl butyrate, methyl acetate,methyl butyrate, methyl caproate, methyl isobutyrate,alpha-methylphenylglycidate, ethyl succinate, isobutyl cinnamate,cinnamyl formate, methyl cinnamate and terpenyl acetate; hydrocarbonssuch as dimethyl naphthalene, dodecane, methyl diphenyl, methylnaphthalene, myrcene, naphthalene, octadecane, tetradecane, tetramethylnaphthalene, tridecane, trimethyl naphthalene, undecane, caryophyllene,1-phellandrene, p-cymene, 1-alphapinene; pyrazines such as2-methoxy-3-isobutyl pyrazine, 2,3-dimethylpyrazine,2,5-dimethyl-pyrazine, 2,6-dimethylpyrazine,3-ethyl-2,5-dimethylpyrazine, 2-ethyl-3,5,6-trimethylpyrazine,3-isoamyl-2,5-dimethylpyrazine, 5-isoamyl-2,3-dimethylpyrazine,2-isoamyl-3,5,6-trimethylpyrazine, isopropyl dimethylpyrazine, methylethylpyrazine, tetramethylpyrazine, trimethylpyrazine; essential oils,such as jasmine absolute, cassia oil, cinnamon bark oil, rose absolute,orris absolute, lemon essential oil, Bulgarian rose, yara yara andvanilla; thiazoles such as those set forth in U.S. Pat. No. 3,769,040including 2,4,5-trimethylthiazole,2-methyl-5-methoxy-4-isobutylthiazole, 2,4-dimethyl-5-acetyl-thiazoleand 2,4-dimethyl-5-ethylthiazole; thiazolines such as those set forth inU.S. Pat. No. 3,816,445 including 2(2-methylthioethyl)-Δ³ -thiazoline,2-secondary butyl-Δ³ -thiazoline; 2-n-butyl-Δ³ -thiazoline,2-isobutyl-Δ³ -thiazoline, 2-pentyl-Δ³ -thiazoline, 2-hexyl-Δ³-thiazoline and 2-benzyl-Δ³ -thiazoline; lactones such as γ-nonalactone;sulfides, e.g., methyl sulfide and other materials such as maltol,acetoin and acetals (e.g., 1,1-diethoxy-ethane, 1,1-dimethoxy-ethane anddimethoxymethane).

The specific flavoring adjuvant selected for use may be either solid orliquid depending upon the desired physical form of the ultimate product,i.e., foodstuff, whether simulated or natural and should, in any event,(i) be organoleptically compatible with the isobutyl substitutedheterocyclic compounds and/or mixtures of same of our invention by notcovering or spoiling the organoleptic properties (aroma and/or taste)thereof; (ii) be non-reactive with the isobutyl substituted heterocycliccompounds and/or mixtures of same of our invention, and (iii) be capableof providing an environment in which the isobutyl substitutedheterocyclic compounds and/or mixtures of same can be dispersed oradmixed to provide a homogeneous medium. In addition, selection of oneor more flavoring adjuvants, as well as the quantities thereof, willdepend upon the precise organoleptic character desired in the finishedproduct. Thus, in the case of flavoring compositions, ingredientselection will vary in accordance with the foodstuff, chewing gum,medicinal product or toothpaste to which the flavor and/or aroma are tobe imparted, modified, altered or enhanced. In contradistinction, in thepreparation of solid products, e.g., simulated foodstuffs, ingredientscapable of providing normally solid compositions should be selected suchas various cellulose derivatives.

As will be appreciated by those skilled in the art, the amount ofisobutyl substituted heterocyclic compounds and/or mixtures of sameemployed in a particular instance can vary over a relatively wide range,depending upon the desired organoleptic effects to be achieved. Thus,correspondingly, greater amounts would be necessary in those instanceswherein the ultimate food composition to be flavored is relatively blandto the taste, whereas relatively minor quantities may suffice forpurposes of enhancing the composition merely deficient in natural flavoror aroma. The primary requirement is that the amount selected beeffective, i.e., sufficient to alter, modify or enhance the organolepticcharacteristics of the parent composition whether foodstuff per se,chewing gum per se, medicinal product per se, toothpaste per se, orflavoring composition.

The use of insufficient quantities of isobutyl substituted heterocycliccompounds and/or mixtures of same will, of course, substantially vitiateany possibility of obtaining the desired results while excess quantitiesprove needlessly costly and in extreme cases, any disrupt theflavor-aroma balance, thus proving self-defeating. Accordingly, theterminology "effective amount" and "sufficient amount" is to be accordeda significance in the context of the present invention consistent withthe obtention of desired flavoring effects.

Thus, and with respect to ultimate food compositions, chewing gumcompositions, medicinal product compositions and toothpastecompositions, it is found that quantities of isobutyl substitutedheterocyclic compounds and/or mixtures of same ranging from a small buteffective amount, e.g., 5.0 parts per million up to about 100 parts permillion based on total composition are suitable. Concentrations inexcess of the maximum quantity stated are not normally recommended sincethey fail to prove commensurate enhancement of organoleptic properties.In those instances, wherein the isobutyl substituted heterocycliccompounds and/or mixtures of same are added to the foodstuff as integralcomponents of a flavoring composition, it is, of course, essential thatthe total quantity of flavoring composition employed be sufficient toyield an effective isobutyl substituted heterocyclic compounds and/ormixtures of same concentration in the foodstuff products.

Food flavoring compositions prepared in accordance with the presentinvention preferably contain the isobutyl substituted heterocycliccompounds and/or mixtures of same in concentrations ranging from about0.1% up to about 15% by weight based on the total weight of the saidflavoring composition.

The composition described herein can be prepared according toconventional techniques well known as typified by cake batters and fruitdrinks and can be formulated by merely admixing the involved ingredientswithin the proportions stated in a suitable blender to obtain thedesired consistency, homogeneity of dispersion, etc. Alternatively,flavoring compositions in the form of particulate solids can beconveniently prepared by mixing the isobutyl substituted heterocycliccompounds and/or mixtures of same with, for example, gum arabic, gumtragacanth, carageenan and the like, and thereafter spray-drying theresultant mixture whereby to obtain the particular solid product.Pre-prepared flavor mixes in powder form, e.g., a fruit-flavored powdermix, are obtained by mixing the dried solid components, e.g., starch,sugar and the like, and isobutyl substituted heterocyclic compoundsand/or mixtures of same in a dry blender until the requisite degree ofuniformity is achieved.

It is presently preferred to combine with the isobutyl substitutedheterocyclic compounds and/or mixtures of same of our invention thefollowing adjuvants:

p-Hydroxybenzyl acetone;

Geraniol;

Cassia Oil;

Acetaldehyde;

Maltol;

Ethyl methyl phenyl glycidate;

Benzyl acetate;

Dimethyl sulfide;

Eugenol;

Vanillin;

Caryophyllene;

Methyl cinnamate;

Guaiacol;

Ethyl pelargonate;

Cinnamaldehyde;

Methyl anthranilate;

5-Methyl furfural;

Isoamyl acetate;

Isobutyl acetate;

Cuminaldehyde;

Alpha ionone;

Cinnamyl formate;

Ethyl butyrate;

Acetic acid;

Gamma-undecalactone;

Naphthyl ethyl ether;

Diacetyl;

Furfural;

Ethyl acetate;

Anethole;

2,3-Dimethyl pyrazine;

2-Ethyl-3-methyl pyrazine;

3-Phenyl-4-pentenal

2-Phenyl-2-hexenal;

2-Phenyl-2-pentenal;

3-Phenyl-4-pentenal diethyl acetal;

Damascone (1-crotonyl-2,2,6-trimethylcyclohexen-1-one)

Damascenone (1-crotonyl-2,2,6-trimethylcyclohexa-1,5-diene)

Beta-cyclohomocitral (2,2,6-trimethyl-cyclohex-1-ene carboxaldehyde)

Isoamyl butyrate;

Cis-3-hexenol-1;

2-Methyl-2-pentenoic acid;

Elemecine (4-allyl-1,2,6-trimethoxy benzene);

Isoelemecine (4-propenyl-1,2,6-trimethoxy benzene); and

2-(4-Hydroxy-4-methylpentyl) norborandiene prepared according to U.S.Application for Letters Pat. No. 461,703, filed on Apr. 17, 1974

2-Methoxy-3-isobutylpyrazine;

2,4,5-Trimethylthiazole;

2-Methyl-5-methoxy-4-isobutylthiazole;

2,4-Dimethyl-5-acetylthiazole;

2,4-Dimethyl-5-ethylthiazole;

2(2-Methylthioethyl)-Δ³ -thiazoline;

2-Secondary butyl-Δ³ thiazoline;

2-n-Butyl-Δ³ -thiazoline;

2-Isobutyl-Δ³ -thiazoline;

2-Pentyl-Δ³ -thiazoline;

2-Hexyl-Δ³ -thiazoline;

2-Benzyl-Δ³ -thiazoline;

2-Secondary butyl thiazole;

2-n-Butyl thiazole;

2-Phenyl-4-pentenal;

Isovaleraldehyde;

2-Phenyl-2-butenal;

4-Methyl-2-phenyl-2-pentenal;

5-Methyl-2-phenyl-2-hexenal;

An additional aspect of our invention provides an organolepticallyimproved smoking tobacco product and additives therefor, as well asmethods of making the same which overcome specific problems heretoforeencountered in which specific desired chocolate-like, cocoa-like andsweet, creamy aroma and flavor prior to smoking and a chocolate-likearoma and more tobacco-like nuances on smoking in the main stream andside stream, are created or enhanced or modified or augmented and may bereadily controlled and maintained at the desired level regardless ofvariations in the tobacco components of the blend.

This invention further provides improved tobacco additives and methodswhereby desirable chocolate-like, cocoa-like and sweet, creamy aroma andflavor prior to smoking and a chocolate-like aroma and more tobacco-likenuances on smoking in the main stream and side stream may be imparted tosmoking tobacco products and may be readily varied and controlled toproduce the desired uniform flavoring characteristics.

In carrying out this aspect of our invention, we add to smoking tobaccomaterials or a suitable substitute therefor (e.g., dried lettuce leaves)an aroma and flavor additive containing as an active ingredient theisobutyl substituted heterocyclic compounds and/or mixtures of same ofour invention.

In addition to the isobutyl substituted heterocyclic compounds and/ormixtures of same of our invention, other flavoring and aroma additivesmay be added to the smoking tobacco material or substitute thereforeither separately or in mixture with the isobutyl substitutedheterocyclic compounds and/or mixtures of same as follows:

I. Synthetic Materials:

Beta-ethyl-cinnamaldehyde;

Eugenol;

Dipentene;

Damascenone;

Maltol;

Ethyl maltol;

Delta undecalactone;

Delta decalactone;

Benzaldehyde;

Amyl acetate;

Ethyl butyrate;

Ethyl valerate;

Ethyl acetate;

2-Hexenol-1;

2-Methyl-5-isopropyl-1,3-nonadiene-8-one;

2,6-Dimethyl-2,6-undecadiene-10-one;

2-Methyl-5-isopropyl acetophenone;

2-Hydroxy-2,5,5-8a-tetramethyl-1-(2-hydroxyethyl)-decahydronaphthalene;

Dodecahydro-3a,6,6-9a-tetramethyl naphtho-(2,1b)-furan;

4-Hydroxy hexanoic acid, gamma lactone; and

Polyisoprenoid hydrocarbons defined in Example V of U.S. Pat. No.3,589,372 issued on June 29, 1971.

II. Natural Oils

Celery seed oil;

Coffee extract;

Bergamot Oil;

Cocoa extract;

Nutmeg oil; and

Origanum oil.

An aroma and flavoring concentrate containing isobutyl substitutedheterocyclic compounds and/or mixtures of same and, if desired, one ormore of the above-indicated additional flavoring additives may be addedto the smoking tobacco material, to the filter or to the leaf or paperwrapper. The smoking tobacco may be shredded, cured, cased and blendedtobacco material or reconstituted tobacco material or tobaccosubstitutes (e.g., lettuce leaves) or mixtures thereof. The proportionsof flavoring additives may be varied in accordance with taste, butinsofar as the enhancement or the imparting of chocolate-like,cocoa-like, nutty, green, burnt roasted and sweet, creamy notes, we havefound that satisfactory results are obtained if the proportion by weightof the sum total of isobutyl substituted heterocyclic compounds and/ormixtures of same to smoking tobacco material is between 250 ppm and1,500 ppm (0.025%-0.15%) of the active ingredients to the smokingtobacco material. We have further found that satisfactory results areobtained if the proportion by weight of the sum total of isobutylsubstituted heterocyclic compounds and/or mixtures of same used toflavoring material is between 2,500 and 15,000 ppm (0.25 %-1.5%).

Any convenient method for incorporating the isobutyl substitutedheterocyclic compounds and/or mixtures of same into the tobacco productmay be employed. Thus, isobutyl substituted heterocyclic compoundsand/or mixtures of same taken alone or along with other flavoringadditives may be dissolved in a suitable solvent such as ethanol,diethyl ether and/or volatile organic solvents, and the resultingsolution may either be spread on the cured, cased and blended tobaccomaterial or the tobacco material may be dipped into such solution. Undercertain circumstances, a solution of isobutyl substituted heterocycliccompounds and/or mixtures of same taken alone or taken further togetherwith other flavoring additives as set forth above, may be applied bymeans of a suitable applicator such as a brush or roller on the paper orleaf wrapper for the smoking product, or it may be applied to the filterby either spraying, or dipping, or coating.

Furthermore, it will be apparent that only a portion of the tobacco orsubstitute therefor need be treated and the thus-treated tobacco may beblended with other tobaccos before the ultimate tobacco product isformed. In such cases, the tobacco treated may have the isobutylsubstituted heterocyclic compounds and/or mixtures of same in excess ofthe amounts or concentrations above indicated so that when blended withother tobaccos, the final product will have the percentage within theindicated range.

In accordance with one specific example of our invention, an aged, curedand shredded domestic burley tobacco is spread with a 20% ethyl alcoholsolution of 2,4,6-triisobutyl-1,3,5-trioxane having the structure:##STR19## in an amount to provide a tobacco composition containing 800ppm by weight of 2,4,6-triisobutyl-1,3,5-trioxane on a dry basis.Thereafter, the alcohol is removed by evaporation and the tobacco ismanufactured into cigarettes by the usual techniques. The cigarette whentreated as indicated has a desired and pleasing aroma which isdetectable in the main and side streams when the cigarette is smoked.This aroma is described as being more tobacco-like and havingchocolate-like and cocoa-like notes.

While our invention is particularly useful in the manufacture of smokingtobacco, such as cigarette tobacco, cigar tobacco and pipe tobacco,other tobacco products formed from sheeted tobacco dust or fines mayalso be used. Likewise, the isobutyl substituted heterocyclic compoundsand/or mixtures of same of our invention can be incorporated withmaterials such as filter tip materials, seam paste, packaging materialsand the like which are used along with tobacco to form a product adaptedfor smoking. Furthermore, the isobutyl substituted heterocycliccompounds and/or mixtures of same can be added to certain tobaccosubstitutes of natural or synthetic origin (e.g., dried lettuce leaves)and, accordingly, by the term "tobacco" as used throughout thisspecification is meant any composition intended for human consumption bysmoking or otherwise, whether composed of tobacco plant parts orsubstituted materials or both.

It will thus be apparent that the isobutyl substituted heterocycliccompounds and/or mixtures of same of our invention can be utilized toalter, modify or enhance sensory properties, particularly organolepticproperties, such as flavor(s) and/or aroma(s) of a wide variety ofconsumable materials including foodstuffs and tobaccos.

The following examples illustrate processes for specifically producingisobutyl substituted heterocyclic compounds and/or mixtures of same ofour invention and also serve to illustrate the organoleptic qualities ofisobutyl substituted heterocyclic compounds and/or mixtures of same and,in addition, the uses of isobutyl substituted heterocyclic compoundsand/or mixtures of same for their organoleptic properties.

EXAMPLE I PREPARATION OF 2,4,6-TRIISOBUTYL-1,3,5-TRIOXANE

Reaction: ##STR20##

Into a one liter, three-necked reaction flask equipped with mechanicalstirrer, condenser, immersion thermometer, "Y" adapter and cold bath isplaced 200 ml of isovaleraldehyde and 100 ml of benzene. The resultingmixture is cooled to about 5° C. using a ice-water bath. 2 Grams ofconcentrated sulfuric acid is then added dropwise to the reactionmixture while it is being agitated using the mechanical stirrer. Thereaction mass heats up to a temperature of about 12° C.

The reaction mass is then stirred for a period of 19 hours at atemperature of about 22° C. The resulting reaction product is made basicby washing with five 20 ml portions of 5% aqueous sodium hydroxide. Theresulting product is then washed to neutral with two 50 ml portions ofwater. The resulting product is then distilled at 95° C. and 1 mm Hgyielding 2,4,6-triisobutyl-1,3,5-trioxane.

FIG. 1 sets forth the NMR spectrum for the resulting product,2,4,6-triisobutyl-1,3,5-trioxane.

FIG. 2 sets forth the infrared spectrum for the resulting product,2,4,6-triisobutyl-1,3,5-trioxane.

FIG. 3 sets forth the mass spectrum for the resulting product,2,4,6-triisobutyl-1,3,5-trioxane.

The resulting material, when added to tobacco, gives rise to achocolate-like, cocoa-like and sweet, creamy flavor and aroma prior tosmoking; and a chocolate-like aroma nuance with more tobacco-likenuances on smoking in the main stream and the side stream. In foodstuffsthe resultant material gives rise to sweet, dairy-like, creamy, vanilla,berry-like, milk chocolate-like and cocoa butter-like aromas and sweet,dairy-like, creamy, vanilla, berry-like, milk chocolate and cocoabutter-like flavor characteristics.

The resulting 2,4,6-triisobutyl-1,3,5-trioxane is then compared withisovaleraldehyde at about the same intensity insofar as their tastecharacteristics are concerned:

At the rate of 10 ppm for 2,4,6-triisobutyl-1,3,5-trioxane;

At the rate of 0.1 ppm for isovaleraldehyde. The2,4,6-triisobutyl-1,3,5-trioxane has a cocoa/floral aroma and taste asfound in dark chocolate. The isovaleraldehyde is substantially weaker inaroma notes at about the same flavor strength for both chemicals. Itsaroma and taste characteristics are more cocoa powder-like. Therefore,both chemicals are completely different in their aroma and tastecharacteristics.

EXAMPLE II PREPARATION OF ISOBUTYL SUBSTITUTED HETEROCYCLIC COMPOUNDS

Reaction: ##STR21##

Into a 500 ml reaction flask equipped with mechanical stirrer, 250 mladdition funnel, thermometer, "Y" adapter, Freidrich condenser andisopropanol/dry ice bath is placed 86.2 ml of aqueous ammonia (0.5moles). The aqueous ammonia is cooled to 3° C. Dropwise, with stirring,is added 43 grams of isovaleraldehyde. On completion of the addition ofthe isovaleraldehyde, the resulting imine forms a solid mass in theaqueous medium which is dispersed at a temperature of about 35° C. Theaddition time of the isovaleraldehyde is 1.5 hours.

The resulting reaction mass is stirred for an additional 1.5 hoursbefore the dropwise addition of 51.9 grams of2(3)-hydroxy-3(2)-pentanone. The reaction between the2(3)-hydroxy-3(2)-pentanone and the imine is carried out for a period oftwo hours. The resulting reaction mass now exists in two phases. Theaqueous phase is extracted with three 100 ml portions of diethyl etherand combined with the organic phase. The combined organic phases arethen washed with three 100 ml portions of saturated sodium chloridesolution.

The resulting product is fractionally distilled at 110° C. and 10 mm Hgto yield a large number of products, one of which is2,4,6-triisobutyl-1,3,5-trioxane.

The NMR spectrum for 2,4,6-triisobutyl-1,3,5-trioxane is set forth inFIG. 1. The IR spectrum for 2,4,6-triisobutyl-1,3,5-trioxane is setforth in FIG. 2. The mass spectrum for 2,4,6-triisobutyl-1,3,5-trioxaneis set forth in FIG. 3.

The mass spectrum is as follows:

    ______________________________________                                        m/e           Relative intensity                                              ______________________________________                                        41            19                                                              43            35                                                              44            12                                                              45            16                                                              57            20                                                              69            69                                                              71            16                                                              85            27                                                              87            100                                                             173           41                                                              258            0                                                              ______________________________________                                    

FIG. 4 represents the NMR spectrum for5-ethyl-4-methyl-2-isobutyl-3-oxazoline resulting from distillation offraction 2-5 followed by GLC preparative chromatography on Carbowax 20M.FIG. 5 represents the infrared spectrum for5-ethyl-4-methyl-2-isobutyl-3-oxazoline. FIG. 6 represents the massspectrum for 5-ethyl-4-methyl-2-isobutyl-3-oxazoline.

FIG. 7 represents the NMR spectrum for4-ethyl-5-methyl-2-isobutyl-3-oxazoline which is peak 1 separated fromfraction 2-5 by preparative GLC using a Carbowax 20M column. FIG. 8represents the infrared spectrum for4-ethyl-5-methyl-2-isobutyl-3-oxazoline. FIG. 9 represents the massspectrum for 4-ethyl-5-methyl-2-isobutyl-3-oxazoline.

EXAMPLE III TOBACCO FORMULATION

A tobacco mixture is produced by admixing the following ingredients:

    ______________________________________                                        Ingredient       Parts by Weight                                              ______________________________________                                        Bright           40.1                                                         Burley           24.9                                                         Maryland         1.1                                                          Turkish          11.6                                                         Stem (flue-cured)                                                                              14.2                                                         Glycerine        2.8                                                          Water            5.3                                                          ______________________________________                                    

Cigarettes are prepared from this tobacco. The following flavorformulation is prepared:

    ______________________________________                                        Ingredient       Parts by Weight                                              ______________________________________                                        Ethyl butyrate   .05                                                          Ethyl valerate   .05                                                          Maltol           2.00                                                         Cocoa extract    26.00                                                        Coffee extract   10.00                                                        Ethyl alcohol    20.00                                                        Water            41.90                                                        ______________________________________                                    

The above-stated tobacco flavor formulation is applied at the rate of0.1% to all of the cigarettes produced using the above tobaccoformulation. Half of the cigarettes are then treated with 500 or 1,000ppm of 2,4,6-triisobutyl-1,3,5-trioxane produced according to theprocess of Example I. The control cigarettes not containing the2,4,6-triisobutyl-1,3,5-trioxane and the experimental cigarettes whichcontain the 2,4,6-triisobutyl-1,3,5-trioxane produced according to theprocess of Example I are evaluated by paired comparison, and the resultsare as follows:

The experimental cigarettes are found, on smoking, to have very pleasantchocolate-like aroma notes and to be more tobacco-like.

The tobacco of the experimental cigarettes, prior to smoking, haschocolate-like, cocoa-like and sweet-creamy notes.

All cigarettes are evaluated for smoke flavor with a 20 mm celluloseacetate filter.

EXAMPLE IV RASPBERRY FLAVOR FORMULATION

The following basic raspberry flavor formulation is produced:

    ______________________________________                                        Ingredient              Parts by Weight                                       ______________________________________                                        Vanillin                2.0                                                   Maltol                  5.0                                                   Parahydroxybenzylacetone                                                                              5.0                                                   Alpha-ionone (10% in propylene glycol)                                                                2.0                                                   Ethyl butyrate          6.0                                                   Ethyl acetate           16.0                                                  Dimethyl sulfide        1.0                                                   Isobutyl acetate        13.0                                                  Acetic acid             10.0                                                  Acetaldehyde            10.0                                                  Propylene glycol        930.0                                                 ______________________________________                                    

2,4,6-Triisobutyl-1,3,5-trioxane is added to half of the aboveformulation at the rate of 5.0%. The formulation with the2,4,6-triisobutyl-1,3,5-trioxane is compared with the formulationwithout the 2,4,6-triisobutyl-1,3,5-trioxane at the rate of 0.01% (100ppm) in water and evaluated by a bench panel.

The flavor containing the 2,4,6-triisobutyl-1,3,5-trioxane is found tohave substantially sweeter aroma notes and a sweet raspberry, raspberrykernel-like and sweet aftertaste and mouthfeel missing in the basicraspberry formulation. It is the unanimous opinion of the bench panelthat the chemical, 2,4,6-triisobutyl-1,3,5-trioxane rounds the flavorout and contributes to a very natural fresh aroma and taste as found infull ripe raspberries.

EXAMPLE V A. POWDER FLAVOR COMPOSITION

70 Grams of the flavor composition of Example IV is emulsified in asolution containing 310 gm gum acacia and 620 gm water. The emulsion isspray-dried with a Bowen Lab Model Drier utilizing 260 c.f.m. of airwith an inlet temperature of 500° F., an outlet temperature of 200° F.,and a wheel speed of 50,000 r.p.m.

B. SUSTAINED RELEASE FLAVOR

The following mixture is prepared:

    ______________________________________                                        Ingredient              Parts by Weight                                       ______________________________________                                        Liquid Raspberry Flavor                                                       Composition of Example IV                                                                             20                                                    Propylene glycol        9                                                     Cab-O-Sil® M-5                                                            (Brand of Silica produced by the Cabot                                        Corporation of 125 High Street, Boston,                                       Mass. 02110;                                                                  Physical Properties:                                                           Surface Area: 200 m.sup.2 /gm                                                 Nominal particle size: 0.012 microns                                          Density: 2.3 lbs/cu.ft.)                                                                             5.00                                                  ______________________________________                                    

The Cab-O-Sil is dispersed in the liquid raspberry flavor composition ofExample IV with vigorous stirring, thereby resulting in a viscousliquid. 71 Parts by weight of the powder flavor composition of Part A,supra, is then blended into the said viscous liquid, with stirring at25° C. for a period of 30 minutes resulting in a dry, free flowingsustained release flavor powder.

EXAMPLE VI SOLID FLAVOR

10 Parts by weight of 50 Bloom pigskin gelatin is added to 90 parts byweight of water at a temperature of 150° F. The mixture is agitateduntil the gelatin is completely dissolved and the solution is cooled to120° F. 20 Parts by weight of the liquid flavor composition of ExampleIV is added to the solution which is then homogenized to form anemulsion having particle size typically in the range of 2-5 microns.This material is kept at 120° F. under which conditions the gelatin willnot gel.

Coascervation is induced by adding, slowly and uniformly, 40 parts byweight of a 20% aqueous solution of sodium sulphate. Duringcoascervation, the gelatin molecules are deposited uniformly about eachoil droplet as a nucleus.

Gelation is effected by pouring the heated coascervate mixture into1,000 parts by weight of 7% aqueous solution of sodium sulphate at 65°F. The resulting jelled coascervate may be filtered and washed withwater at temperatures below the melting point of gelatin, to remove thesalt.

Hardening of the filtrate, in this example, is effected by washing with200 parts by weight of 37% solution of formaldehyde in water. The cakeis then washed to remove residual formaldehyde.

EXAMPLE VII CHEWING GUM

100 Parts by weight of chicle are mixed with 4 parts by weight of theflavor prepared in accordance with Example V. 300 Parts of sucrose and100 parts of corn syrup are added. Mixing is effected in a ribbonblender with jacketed side walls of the type manufactured by the BakerPerkins Co.

The resultant chewing gum blend is then manufactured into strips 1 inchin width and 0.1 inches in thickness. The strips are cut into lengths of3 inches each. On chewing, the chewing gum has a pleasant, long-lastingraspberry flavor.

EXAMPLE VIII CHEWING GUM

100 Parts by weight of chicle are mixed with 18 parts by weight of theflavor prepared in accordance with Example VI. 300 Parts of sucrose and100 parts of corn syrup are then added. Mixing is effected in a ribbonblender with jacketed side walls of the type manufactured by the BakerPerkins Co.

The resultant chewing gum blend is then manufactured into strips 1 inchin width and 0.1 inches in thickness. The strips are cut into lengths of3 inches each. On chewing, the chewing gum has a pleasant, long-lastingraspberry flavor.

EXAMPLE IX TOOTHPASTE FORMULATION

The following separate groups of ingredients are prepared:

    ______________________________________                                        Parts by Weight                                                                         Ingredient                                                          ______________________________________                                        Group "A"                                                                     30.200    Glycerin                                                            15.325    Distilled Water                                                      .100     Sodium Benzoate                                                      .125     Saccharin Sodium                                                     .400     Stannous Flouride                                                   Group "B"                                                                     12.500    Calcium Carbonate                                                   37.200    Dicalcium Phosphate (Dihydrate)                                     Group "C"                                                                     2.000     Sodium K-Lauroyl Sarcosinate (foaming agent)                        Group "D"                                                                     1.200     Flavor Material of Example V                                        100.00 (Total)                                                                PROCEDURE:                                                                    1.  The ingredients in Group "A" are stirred and heated in a                      steam jacketed kettle to 160° F.                                   2.  Stirring is continued for an additional three to five                         minutes to form a homogenous gel.                                         3.  The powders of Group "B" are added to the gel, while                          mixing until a homogenous paste is formed.                                4.  With stirring, the flavor of "D" is added and lastly the                      sodium n-laureyl sarcosinate.                                             5.  The resultant slurry is then blended for n-lauroyl hour. The                  completed paste is then transferred to a three roller                         mill and then homogenized, and finally tubed.                             ______________________________________                                    

The resulting toothpaste when used in a normal toothbrushing procedureyields a pleasant raspberry flavor, of constant strong intensitythroughout said procedure (1-1.5 minutes).

EXAMPLE X CHEWABLE VITAMIN TABLETS

The flavor material produced according to the process of Example VI isadded to a Chewable Vitamin Tablet Formulation at a rate of 10 gm/Kgwhich Chewable Vitamin Tablet Formulation is prepared as follows:

In a Hobart Mixer, the following materials are blended to homogeneity:

    ______________________________________                                                               Gms/1000                                                                      tablets                                                ______________________________________                                        Vitamin C (ascorbic acid)                                                     as ascorbic acid-sodium ascorbate mixture 1:1                                                          70.0                                                 Vitamin B.sub.1 (thiamine mononitrate)                                        as Rocoat® thiamine mononitrate 33 1/3%                                   (Hoffman La Roche)       4.0                                                  Vitamin B.sub.2 (riboflavin)                                                  as Rocoat® riboflavin 33 1/3%                                                                      5.0                                                  Vitamin B.sub.6 (pyridoxine hydrochloride)                                    as Rocoat® pyridoxine hydrochloride 33 1/3%                                                        4.0                                                  Niacinamide                                                                   as Rocoat® niacinamide 33 1/3%                                                                     33.0                                                 Calcium pantothenate     11.5                                                 Vitamin B.sub.12 (cyanocobalamin)                                             as Merck 0.1% in gelatin 3.5                                                  Vitamin E (dl-alpha tocopheryl acetate)                                       as dry Vitamin E acetate 33 1/3% Roche                                                                 6.6                                                  d-Biotin                 0.044                                                Certified lake color     5.0                                                  Flavor of Example VI     (as indicated                                                                 above)                                               Sweetener - sodium saccharin                                                                           1.0                                                  Magnesium stearate lubricant                                                                           10.0                                                 Mannitol q.s. to make    500.0                                                ______________________________________                                    

Preliminary tablets are prepared by slugging with flat-faced punches andgrinding the slugs to 14 mesh. 13.5 g dry Vitamin A Acetate and 0.6 gVitamin D are then added as beadlets. The entire blend is thencompressed using concave punches at 0.5 g each.

Chewing of the resultant tablets yields a pleasant, long-lasting,consistently strong raspberry flavor for a period of 12 minutes.

EXAMPLE XI CHEWING TOBACCO

Onto 100 pounds of tobacco for chewing (85% Wisconsin leaf and 15%Pennsylvania leaf) the following casing is sprayed at a rate of 30%:

    ______________________________________                                        Ingredients       Parts by Weight                                             ______________________________________                                        Corn Syrup        60                                                          Licorice          10                                                          Glycerine         20                                                          Fig Juice         4.6                                                         Prune Juice       5                                                           Flavor Material of                                                            Example V         0.4                                                         ______________________________________                                    

The resultant product is redried to a moisture content of 20%. Onchewing, this tobacco has an excellent substantially consistent,long-lasting raspberry (20 minutes) nuance in conjunction with the mainfruity tobacco note.

EXAMPLE XII COCOA FLAVOR

The following basic cocoa formulation is prepared by admixing thefollowing ingredients:

    ______________________________________                                        Ingredients          Parts by Weight                                          ______________________________________                                        Vanillin             6.5                                                      Amylphenyl acetate   3.5                                                      Benzyl butyrate      0.5                                                      Veratraldehyde       0.5                                                      5-Methyl-2-phenyl-2-hexenal                                                                        3.0                                                      Isovaleraldehyde     4.0                                                      Isobutyraldehyde     1.0                                                      Benzaldehyde         0.2                                                      5-Methyl furfural    0.8                                                      Propylene glycol     80.0                                                     ______________________________________                                    

The foregoing flavor formulation is divided into two portions. To afirst portion, 10% by weight of 2,4,6-triisobutyl-1,3,5-trioxaneprepared according to Example I, is added. Nothing is added to thesecond portion. Both flavors are compared at the rate of 20 ppm inwater. The flavor containing the 2,4,6-triisobutyl-1,3,5-trioxane has acharacteristic cocoa-butter note, both in aroma and in taste. Thischaracteristic cocoa-butter note is missing in the basic flavorformulation without said 2,4,6-triisobutyl-1,3,5-trioxane. Therefore, abench panel, composed of three individuals, prefers the formulationwhich contains the 2,4,6-triisobutyl-1,3,5-trioxane.

EXAMPLE XIII CHOCOLATE FORMULATION

The following basic chocolate formulation is prepared:

    ______________________________________                                        Ingredients          Parts by Weight                                          ______________________________________                                        Maltol               0.30                                                     Isobutyraldehyde     1.50                                                     Isovaleraldehyde     4.20                                                     Propylene glycol     3.00                                                     Dimethyl sulfide     0.05                                                     Isobutyl acetate     0.10                                                     Isoamyl acetate      0.20                                                     Phenylethyl acetate  0.05                                                     Diacetyl (10% in food grade                                                   ethyl alcohol)       0.50                                                     Furfural (10% in food grade                                                   ethyl alcohol)       0.10                                                     Benzaldehyde         0.10                                                     Isoamyl alcohol      0.05                                                     Phenylethyl alcohol  0.30                                                     ______________________________________                                    

In addition, a chocolate-like flavor composition is prepared with thefollowing ingredients:

    ______________________________________                                        Ingredients         Parts by Weight                                           ______________________________________                                        Trimethylthiazole (10% in                                                     food grade ethyl                                                              alcohol)            2.0                                                       Tetramethylpyrazine 4.0                                                       2,4,6-Triisobutyl-1,3,5-                                                      trioxane (prepared                                                            according to Example I)                                                                           2.0                                                       Food grade ethanol  2.0                                                       ______________________________________                                    

The basic chocolate formulation is divided into two portions. To a firstportion, 10% by weight of the "chocolate-like flavor composition"containing the 2,4,6-triisobutyl-1,3,5-trioxane, is added. To the secondportion, nothing is added. Both flavors with and without the additionalmaterial are compared at the rate of 20 ppm in water. The flavor withthe additional "chocolate-like flavor composition" has a full darkchocolate aroma and taste with a sweet, milk chocolate undertone. Thesenotes are missing in the basic formulation without the addition of the"chocolate-like flavor composition". The added "chocolate-like flavorcomposition" causes the "basic chocolate formulation" to be preferred bya bench panel composed of three individuals.

EXAMPLE XIV COCOA FLAVOR

The following basic cocoa formulation is prepared:

    ______________________________________                                        Ingredients          Parts by Weight                                          ______________________________________                                        Vanillin             6.5                                                      Amylphenyl acetate   3.5                                                      Benzyl butyrate      0.5                                                      Veratraldehyde       0.5                                                      5-Methyl-2-phenyl-2-hexenal                                                                        3.0                                                      Isovaleraldehyde     4.0                                                      Isobutyraldehyde     1.0                                                      Benzaldehyde         0.2                                                      5-Methyl furfural    0.8                                                      Propylene glycol     80.0                                                     ______________________________________                                    

The above basic cocoa formulation is divided into two portions. To afirst portion, 7.5% by weight of4-ethyl-2-isobutyl-5-methyl-3-oxazoline, prepared according to ExampleII, is added. To the second portion, nothing is added. Both flavorformulations with and without the additional4-ethyl-2-isobutyl-5-methyl-3-oxazoline, are compared at the rate of 20ppm in water. The flavor containing the4-ethyl-2-isobutyl-5-methyl-3-oxazoline has a deeper, cocoa character,more mouthfeel and a "light hydrolyzed vegetable protein-like" note. Itis therefore preferred by a bench panel composed of three individuals.

EXAMPLE XV TOBACCO FORMULATION

A tobacco mixture is produced by admixing the following ingredients:

    ______________________________________                                        Ingredients      Parts by Weight                                              ______________________________________                                        Bright           40.1                                                         Burley           24.9                                                         Maryland         1.1                                                          Turkish          11.6                                                         Stem (flue-cured)                                                                              14.2                                                         Glycerine        2.8                                                          Water            5.3                                                          ______________________________________                                    

Cigarettes are prepared from this tobacco.

The following flavor formulation is prepared:

    ______________________________________                                        Ingredients     Parts by Weight                                               ______________________________________                                        Ethyl butyrate  .05                                                           Ethyl valerate  .05                                                           Maltol          2.00                                                          Cocoa extract   26.00                                                         Coffee extract  10.00                                                         Ethyl alcohol   20.00                                                         Water           41.90                                                         ______________________________________                                    

The above-stated tobacco flavor formulation is applied at the rate of0.1% to all of the cigarettes produced using the above tobaccoformulation. Half of the cigarettes are then treated with 500 or 1,000ppm of 4-ethyl-2-isobutyl-5-methyl-3-oxazoline produced according to theprocess of Example II. The control cigarettes not containing the4-ethyl-2-isobutyl-5-methyl-3-oxazoline and the experimental cigaretteswhich contain the said oxazoline produced according to the process ofExample II are evaluated by paired comparison, and the results are asfollows:

The experimental cigarettes are found, on smoking, to have very pleasantchocolate-like, nutty, green and burnt roasted-like aroma notes and tobe more tobacco-like.

The tobacco of the experimental cigarettes, prior to smoking, haschocolate-like, nutty, green notes.

All cigarettes are evaluated for smoke flavor with a 20 mm celluloseacetate filter.

EXAMPLE XVI USE OF 5-ETHYL-4-METHYL-2-ISOBUTYL-3-OXAZOLINE TO ENHANCETHE VEGETABLE FLAVOR OF VEGETARIAN VEGETABLE SOUP

5-Ethyl-4-methyl-2-isobutyl-3-oxazoline produced according to Example IIis added at the rate of 2 ppm to condensed vegetarian vegetable soup(Shop-Rite® brand). One liter of water is added to one liter of soup andthoroughly admixed. The resulting mixture is then simmered(temperature=200° F.) for a period of ten minutes. The resulting soup iscompared by a bench panel with a soup which has no5-ethyl-4-methyl-2-isobutyl-3-oxazoline added thereto. The soup havingthe 5-ethyl-4-methyl-2-isobutyl-3-oxazoline prepared according toExample II is unanimously preferred as having a more vegetable-liketaste with excellent cooked green pepper, spicey, peppery and meatyaroma and taste nuances.

What is claimed is:
 1. A process for augmenting or enhancing the aromaor taste of a smoking tobacco comprising the step of adding to saidsmoking tobacco an organoleptic property augmenting or enhancingquantity of a mixture of isobutyl substituted heterocyclic compoundshaving the generic formula: ##STR22## wherein X is a moiety selectedfrom the group consisting of: ##STR23## and wherein R₁ and R₂ aredifferent and each is selected from the group consisting of methyl andethyl, consisting of (i) 2,4,6-triisobutyl-1,3,5-trioxane having theformula: ##STR24## and (ii) a mixture of oxazoline compounds having thegeneric structure: ##STR25## wherein R₁ and R₂ are different and each isselected from the group consisting of ethyl and methyl.
 2. A smokingtobacco composition comprising smoking tobacco and intimately admixedtherewith a composition useful in augmenting or enhancing the aroma ortaste of said smoking tobacco consisting of (i) a smoking tobacco flavoraugmenting or enhancing quantity of a mixture of isobutyl substitutedheterocyclic compounds having the generic formula: ##STR26## and whereinX is a moiety selected from the group consisting of: ##STR27## andwherein R₁ and R₂ are different and each is selected from the groupconsisting of methyl and ethyl, comprising (a)2,4,6-triisobutyl-1,3,5-trioxane having the formula: ##STR28## and (b) amixture of oxazoline compounds having the generic structure: ##STR29##wherein R₁ and R₂ are different and each is selected from the groupconsisting of ethyl and methyl; and (ii) the remainder of saidformulation being at least one adjuvant for said mixture beingcompatible with said mixture and said smoking tobacco and being selectedfrom the group consisting of:Beta-ethyl-cinnamaldehyde; Eugenol;Dipentene; Damascenone; Maltol; Ethyl maltol; Delta decalactone;Benzaldehyde; Amyl acetate; Ethyl butyrate; Ethyl valerate; Ethylacetate; 2-Hexenol-1; 2-Methyl-5-isopropyl-1,3-nonadiene-8-one;2,6-Dimethyl-2,6-undecadiene-10-one; 2-Methyl-5-isopropyl acetophenone;2-Hydroxy-2,5,5-8a-tetramethyl-1-(2-hydroxyethyl)-decahydronaphthalene;Dodecahydro-3a,6,6-9a-tetramethyl naphtho(2,1b)-furan; 4-Hydroxyhexanoic acid, gamma lactone; Polyisoprenoid hydrocarbons; Celery seedoil; Coffee extract; Bergamot oil; Cocoa extract; Nutmeg oil; andOriganum oil.